Hard mask and process for forming the same by plasma enhanced chemical vapor deposition

Abstract

Embodiments of the present disclosure generally relate to hardmasks and processes for forming hardmasks by plasma-enhanced chemical vapor deposition (PECVD). In one embodiment, a process for forming a hardmask layer on a substrate is provided. The process includes introducing a substrate into a processing volume of a PECVD chamber, the substrate being on a substrate support, the substrate support including an electrostatic chuck; and flowing a process gas into the processing volume within the PECVD chamber, the process gas including a carbon-containing gas. The process further includes forming an energized process gas from the process gas in the processing volume under plasma conditions, electrostatically clamping the substrate to the substrate support, depositing a first carbon-containing layer on the substrate while electrostatically clamping the substrate, and forming the hardmask layer by depositing a second carbon-containing layer on the substrate.

Description

[0001] background

[0002] field

[0003] Embodiments of the present disclosure generally relate to hardmasks and processes for forming hardmasks by plasma enhanced chemical vapor deposition. Background Art

[0004] Carbon-based hard molds are commonly used for resist masks in patterning and line width trimming applications due to reasons such as the mechanical properties of carbon-based hard molds. Carbon-based hard molds are typically manufactured by plasma enhanced chemical vapor deposition (PECVD). Traditionally, the plasma conditions for forming such hard molds only use argon and / or helium. However, under plasma conditions, high energy bombardment of materials such as argon and / or helium can damage the underlying dielectric material on which the hard mold is formed, particularly during substrate clamping. Damage to the underlying dielectric material can lead to deterioration of device performance.

[0005] New and improved processes are needed that mitigate underlying layer damage, for example, during hardmask formation. Summary of the Invention

[0006] Embodiments of the present disclosure generally relate to hardmasks and processes for forming hardmasks by PECVD. Embodiments described herein reduce or eliminate underlying layer damage during hardmask formation and improve adhesion between the hardmask and the substrate.

[0007] In one embodiment, a process for forming a hardmask layer on a substrate is provided. The process includes introducing a substrate into a processing volume of a PECVD chamber, the substrate being on a substrate support, the substrate support including an electrostatic chuck; and flowing a process gas into the processing volume within the PECVD chamber, the process gas including a carbon-containing gas. The process further includes forming an energized process gas from the process gas in the processing volume under plasma conditions, electrostatically chucking the substrate to the substrate support, depositing a first carbon-containing layer on the substrate while electrostatically chucking the substrate, and forming the hardmask layer by depositing a second carbon-containing layer on the substrate.

[0008] In another embodiment, a process for forming a hard mask layer on a substrate is provided. The process includes introducing a substrate into a processing volume of a PECVD chamber, the substrate being on a substrate support, the substrate support including an electrostatic chuck; and flowing a process gas into the processing volume within the PECVD chamber. The process gas includes a carbon-containing gas, wherein the carbon-containing gas includes or is formed from a carbon-containing compound, and wherein the carbon-containing compound is a substituted or unsubstituted C1-C 40 Hydrocarbons, substituted or unsubstituted C6-C 20 Aromatic hydrocarbons, C1-C 40A halogenated hydrocarbon, or a combination thereof. The process further includes forming an energized process gas from a process gas in a process volume under plasma conditions, electrostatically clamping the substrate to a substrate support, depositing a first carbon-containing layer on the substrate while electrostatically clamping the substrate, and forming a hardmask layer by depositing a second carbon-containing layer on the substrate. The first carbon-containing layer, the second carbon-containing layer, or both are deposited while the substrate is maintained at a temperature of about -40°C to about 40°C and a pressure in the process volume of about 1 mTorr to about 20 mTorr, or a combination thereof.

[0009] In another embodiment, a process for forming a hard mask layer on a substrate is provided. The process includes introducing a substrate into a processing volume of a PECVD chamber, the substrate being on a substrate support, the substrate support including an electrostatic chuck; and flowing a process gas into the processing volume within the PECVD chamber. The process gas includes a carbon-containing gas, wherein the carbon-containing gas includes or is formed from a carbon-containing compound, wherein the carbon-containing compound includes Cl-C 20 The process further includes forming an energized process gas from a process gas in the process volume under plasma conditions, the plasma conditions comprising applying an RF bias power of about 200 W to about 5000 W to a substrate support, electrostatically clamping the substrate to the substrate support, depositing a first carbon-containing layer on the substrate while electrostatically clamping the substrate, and forming a hardmask layer by depositing a second carbon-containing layer on the substrate. The first carbon-containing layer, the second carbon-containing layer, or both are deposited while the substrate is maintained at a temperature of about -40°C to about 40°C and a pressure within the process volume of about 1 mTorr to about 20 mTorr, or a combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] In order that the manner in which the above-described features of the present disclosure can be understood in detail, the present disclosure, briefly summarized above, may be described in more detail by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of the scope thereof, and that other equally effective embodiments may be admitted.

[0011] Figure 1 is a schematic side cross-sectional view of an example processing chamber according to at least one embodiment of the present disclosure.

[0012] Figure 2A is a schematic cross-sectional view of an example substrate support according to at least one embodiment of the present disclosure.

[0013] Figure 2B According to at least one embodiment of the present disclosure Figure 2A An enlarged cross-sectional view of a portion of an example substrate support is shown in FIG.

[0014] Figure 3 is a flowchart illustrating selected operations of an example method of processing a substrate in accordance with at least one embodiment of the present disclosure.

[0015] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation. DETAILED DESCRIPTION

[0016] Embodiments of the present disclosure generally relate to hard molds and processes for forming hard molds by PECVD. The inventors have discovered new and improved processes and resulting hard mold structures that overcome one or more deficiencies of conventional methods of forming hard molds. For example, the embodiments described herein reduce substrate damage during hard mold formation and improve adhesion between the hard mold and the surface on which the hard mold is disposed. Briefly, in some examples, a substrate is electrostatically clamped to a substrate support in the presence of a carbon-containing gas. A first carbon-containing layer is formed while the substrate is electrostatically clamped. The substrate is then provided with a second carbon-containing layer (e.g., a diamond-like carbon (DLC) film or a sp-type carbon having greater than 60% carbon) by depositing the second carbon-containing layer on the substrate. 3 The resulting carbon-containing layer can prevent or at least mitigate damage to the underlying layer caused by high-energy ion bombardment and reduce impact on the wafer.

[0017] Conventional plasma ignition methods (e.g., ignition) typically utilize only non-reactive gases (e.g., argon or helium), while the main deposition operation utilizes a precursor / carrier (e.g., acetylene / helium) mixture. As a result, high-energy bombarding ions impact the dielectric layer below the carbon hardmask before the carbon hardmask is formed on the dielectric layer. In contrast, the embodiments described herein utilize a carbon-containing gas (with or without a non-reactive gas) to ignite the plasma and form the initiation layer while electrostatically clamping the substrate. During the deposition operation, the carbon-containing gas (with or without a non-reactive gas) can be used to form the carbon hardmask. After removing the carbon-based hardmask, a wavy morphology of the resulting dielectric material can be observed. In contrast, the embodiments described herein eliminate or at least reduce damage to the underlying dielectric material. Therefore, the embodiments described herein can achieve, for example, improved device performance.

[0018] Figure 1is a schematic side cross-sectional view of an example processing chamber 100 suitable for performing a deposition process in accordance with at least one embodiment. Suitable chambers are available from Applied Materials, Inc., located in Santa Clara, California. It should be understood that the system described below is an exemplary processing chamber and that other chambers (including chambers from other manufacturers) can be used with or modified to accomplish embodiments of the present disclosure (e.g., process 300 described below). In some embodiments, the processing chamber 100 can be configured to deposit advanced patterned films, such as hard mask films, e.g., amorphous carbon hard mask films, onto a substrate.

[0019] The processing chamber 100 includes a lid assembly 105, a spacer 110 disposed on a chamber body 192, a substrate support 115, and a variable pressure system 120. The lid assembly 105 includes a lid plate 125 and a heat exchanger 130. In the illustrated embodiment, the lid assembly 105 also includes a showerhead 135. However, in other embodiments, the lid assembly 105 includes a concave or dome-shaped gas introduction plate.

[0020] The lid assembly 105 is coupled to a first process gas source 140. The first process gas source 140 contains a precursor gas for forming a film on a substrate 145 supported on a substrate support 115. As an example, the first process gas source 140 includes a precursor gas such as a carbon-containing gas, a hydrogen-containing gas, a non-reactive gas (e.g., helium), and the like. In a specific example, the carbon-containing gas includes acetylene (C2H2). The first process gas source 140 provides the precursor gas to a gas chamber 190 disposed in the lid assembly 105. The lid assembly includes one or more channels for directing the precursor gas from the first process gas source 140 into the gas chamber 190. The precursor gas flows from the gas chamber through the showerhead 135 into the processing volume 160. In some embodiments, a second process gas source 142 is fluidly coupled to the processing volume 160 via an inlet 144 disposed through the spacer 110. As an example, the second process gas source 142 includes a precursor gas, such as C2H2, such as a carbon-containing gas, a hydrogen-containing gas, a non-reactive gas (e.g., helium), and the like. In some embodiments, the total flow rate of the precursor gas entering the processing space 160 is about 100 seem to about 2 slm. The flow of the precursor gas in the processing space 160 via the second process gas source 142 regulates the flow of the precursor gas flowing through the showerhead 135, so that the precursor gas is evenly distributed in the processing space 160. In one example, the plurality of inlets 144 can be distributed radially around the spacer 110. In such an example, the gas flowing to each of the inlets 144 can be individually controlled to further promote gas uniformity within the processing space 160.

[0021] The lid assembly 105 may also be coupled to an optional remote plasma source 150. The optional remote plasma source 150 is coupled to a cleaning gas source 155 to provide a cleaning gas to a processing volume 160 formed within the spacer 110 between the lid assembly 105 and the substrate 145. In one example, the cleaning gas is provided through a central conduit 191 formed axially through the lid assembly 105. In another example, the cleaning gas is provided through the same channel that guides the precursor gas. Example cleaning gases include oxygen-containing gases (such as oxygen and / or ozone) and fluorine-containing gases (such as NF3), or combinations thereof.

[0022] In addition to or in lieu of the optional remote plasma source 150, the lid assembly 105 may also be coupled to a first or upper radio frequency (RF) power source 165. The first RF power source 165 facilitates maintaining or generating a plasma, such as a plasma generated by a cleaning gas. In one example, the optional remote plasma source 150 is omitted, and the cleaning gas is ionized into a plasma in situ via the first RF power source 165. The substrate support 115 is coupled to a second or lower RF power source 170. The first RF power source 165 can be a high-frequency RF power source (e.g., from about 13.56 MHz to about 120 MHz), while the second RF power source 170 can be a low-frequency RF power source (e.g., from about 2 MHz to about 13.56 MHz). It should be noted that other frequencies are also contemplated. In some embodiments, the second RF power source 170 is a mixed-frequency RF power source that provides both high-frequency and low-frequency power. Utilizing a dual-frequency RF power source, particularly the second RF power source 170, can improve film deposition. In some examples, the second RF power source 170 is utilized to provide dual-frequency power. In some embodiments, a first frequency, for example, about 2 MHz to about 13.56 MHz, improves infusion of species into the deposited film, while a second frequency, for example, about 13.56 MHz to about 120 MHz, increases ionization and film deposition rate.

[0023] One or both of the first RF power source 165 and the second RF power source 170 can be used to generate or maintain a plasma in the processing volume 160. For example, the second RF power source 170 can be used during a deposition process, while the first RF power source 165 can be used during a cleaning process (alone or in combination with the optional remote plasma source 150). In some deposition processes, the first RF power source 165 and the second RF power source 170 are used in combination. During a deposition or etching process, one or both of the first RF power source 165 and the second RF power source 170 can provide power in the processing volume 160, for example, from about 100 watts (W) to about 20,000 W, to promote ionization of the precursor gas. In some embodiments, at least one of the first RF power source 165 and the second RF power source 170 is pulsed. In at least one embodiment, RF power is applied to the cover plate 125.

[0024] The substrate support 115 is coupled to an actuator 175 (i.e., a lift actuator) that provides movement of the substrate support 115 in the Z direction. The substrate support 115 is also coupled to a facility cable 178 that is flexible and allows vertical movement of the substrate support 115 while maintaining communication with the second RF power source 170 and other power and fluid connections. A spacer 110 is disposed on the chamber body 192. The height of the spacer 110 allows the substrate support 115 to move vertically within the processing volume 160. The height of the spacer 110 is about 0.5 inches to about 20 inches. In one example, the substrate support 115 can be moved from a first distance 180A relative to the lid assembly 105 (e.g., relative to the lower surface of the showerhead 135) to a second distance 180B. In some embodiments, the second distance 180B is about 2 / 3 of the first distance 180A. For example, the difference between the first distance 180A and the second distance is about 5 inches to about 6 inches. Therefore, from Figure 1 Starting from the position shown, the substrate support 115 is movable from about 5 inches to about 6 inches relative to the lower surface of the showerhead 135. In another example, the substrate support 115 is fixed at one of a first distance 180A and a second distance 180B. Compared to conventional plasma enhanced chemical vapor deposition (PECVD) processes, the spacer 110 significantly increases the distance between the substrate support 115 and the lid assembly 105 (and therefore significantly increases the volume between the substrate support 115 and the lid assembly 105). The increased distance between the substrate support 115 and the lid assembly 105 reduces collisions of ionized species in the processing volume 160, resulting in the deposition of films with lower neutral stress, such as less than 2.5 gigapascals (GPa). Films deposited with lower neutral stress facilitate improved planarity (e.g., less bow) of the substrate on which the film is formed. Reduced substrate bow results in increased precision in downstream patterning operations.

[0025] The variable pressure system 120 includes a first pump 182 and a second pump 184. The first pump 182 is a roughing pump that can be used during the cleaning process and / or substrate transfer process. Roughing pumps are typically configured to move higher volumetric flows and / or operate at relatively high (although still below atmospheric) pressures. In a non-limiting example, the first pump 182 maintains the pressure in the processing chamber at less than 500 mTorr, such as less than about 50 mTorr, during the cleaning process. In another example, the first pump 182 maintains the pressure in the processing chamber 100 at, for example, less than about 500 mTorr, such as less than about 50 mTorr, such as about 0.5 mTorr to about 10 Torr or about 5 mTorr to about 15 mTorr. Using a roughing pump during the cleaning operation facilitates a relatively high pressure and / or volumetric flow of the cleaning gas (compared to the deposition operation). During the cleaning operation, the relatively high pressure and / or volumetric flow improves the cleaning of the chamber surface.

[0026] The second pump 184 can be a turbo pump and a cryogenic pump. The second pump 184 can be used during the deposition process. The second pump 184 is generally configured to operate at a relatively low volume flow rate and / or pressure. In a non-limiting example, the second pump 184 is configured to maintain the processing space 160 of the processing chamber at a pressure of less than 500 mTorr, such as less than 50 mTorr. In another example, the second pump 184 maintains the pressure within the processing chamber 100 at, for example, less than about 500 mTorr, such as less than about 50 mTorr, such as from about 0.5 mTorr to about 10 Torr or from about 5 mTorr to about 15 mTorr. When depositing a carbon-based hard mold, maintaining a lower pressure in the processing space 160 during deposition helps to deposit a carbon-based hard mold with a reduced neutral stress and / or increased sp 2 -sp 3 Thus, the processing chamber 100 is configured to utilize both relatively low pressures to improve deposition and relatively high pressures to improve cleaning.

[0027] In some embodiments, both the first pump 182 and the second pump 184 are utilized during the deposition process to maintain the processing volume 160 of the processing chamber at a pressure of less than about 500 mTorr, such as less than about 50 mTorr. In other embodiments, the first pump 182 and the second pump 184 maintain the processing volume 160 at a pressure of, for example, from about 0.5 mTorr to about 10 Torr or from about 5 mTorr to about 15 mTorr. Valve 186 is used to control the conduction path to one or both of the first pump 182 and the second pump 184. Valve 186 also provides symmetrical evacuation of the processing volume 160.

[0028] The processing chamber 100 also includes a substrate transfer port 185. The substrate transfer port 185 is selectively sealed by an inner door 186A and an outer door 186B. Each of the doors 186A and 186B is coupled to an actuator 188 (i.e., a door actuator). The doors 186A and 186B facilitate vacuum sealing of the processing volume 160. The doors 186A and 186B also provide symmetrical RF application and / or plasma symmetry within the processing volume 160. In one example, at least the door 186A is formed of a material that facilitates RF power conduction, such as stainless steel, aluminum, or an alloy thereof. A seal 116 (such as an O-ring) provided at the interface between the spacer 110 and the chamber body 192 can further seal the processing volume 160. A controller 194 coupled to the processing chamber 100 is configured to control various aspects of the processing chamber 100 during processing.

[0029] Figure 2A is a schematic cross-sectional view of one embodiment of a substrate support 115 . Figure 2B yes Figure 2A . As described above, the substrate support 115 may include an electrostatic chuck 230. The electrostatic chuck 230 includes a disk 260. The disk 260 includes one or more electrodes 205 embedded therein (a first electrode 205A and a second electrode 205B are shown in FIG. Figure 2B ). The first electrode 205A serves as a clamping electrode, while the second electrode 205B serves as an RF bias electrode. The substrate support 115 can be biased by supplying RF power to the second electrode 205B at a frequency of, for example, about 300 kHz to about 120 MHz, such as about 300 kHz to about 60 MHz. The frequency supplied to the second electrode 205B can be pulsed. The disk 260 is typically formed of a dielectric material, such as a ceramic material, for example, aluminum nitride (AlN).

[0030] The disk 260 is supported by the dielectric plate 210 and the base plate 215. The dielectric plate 210 may be made of an electrically insulating material such as quartz or a thermoplastic material such as The base plate 215 is formed of a high-performance plastic (a material sold under the trademark EMI shield). The base plate 215 can be made of a metallic material such as aluminum. During operation, when the disk 260 is in an RF heat state, the base plate 215 is coupled to ground or placed in an electrically floating state. At least the disk 260 and the dielectric plate 210 are surrounded by an insulating ring 220. The insulating ring 220 can be made of a dielectric material such as quartz, silicon, or a ceramic material. A portion of the base plate 215 and the insulating ring 220 are surrounded by a grounding ring 225 made of aluminum. The insulating ring 220 prevents or minimizes arcing between the disk 260 and the base plate 215 during operation. One end of the facility cable 178 is shown in an opening formed in the disk 260, the dielectric plate 210, and the base plate 215. Power for the electrodes of the disk 260 and fluid from a gas source (not shown) to the substrate support 115 are provided by the facility cable 178.

[0031] An edge ring (not shown) is disposed adjacent the inner periphery of the insulating ring 220. The edge ring may include dielectric materials such as quartz, silicon, cross-linked polystyrene, and divinylbenzene (such as ), PEEK, Al2O3, AIN, etc. Using edge rings comprising such dielectric materials helps to modulate plasma coupling, modulate plasma properties such as the voltage on the substrate support (V dc )) without changing the plasma power, thereby improving the properties of the hard mask film deposited on the substrate. Modulating the RF coupling to the wafer or substrate through the material of the edge ring can decouple the modulus of the film from the stress of the film.

[0032] Each of the disk 260, dielectric plate 210, and base plate 215 includes an axially aligned opening formed therein or therethrough, respectively, for receiving the service cable 178. The disk 260 includes an opening 295 shaped to engage the service cable 178. For example, the opening 295 can be configured as a receptacle for receiving the service cable 178. The dielectric plate 210 includes an opening 296 axially aligned with the opening 295. The opening 296 includes an upper portion 296a having a diameter approximately equal to the diameter of the opening 295, a middle portion 296b having a larger diameter than the upper portion, and a lower portion 296c having a larger diameter than the middle portion 296b. The base plate 215 includes an opening 297 having an upper portion 297a and a lower portion 297b. The upper portion 297a has a first diameter and the lower portion 297b has a second diameter that is smaller than the first diameter. The multiple diameters of openings 296 and 297 may help secure service cable 178 therein.

[0033] The disk 260 includes a plurality of fluid channels 231 formed therein. Each fluid channel 231 is in fluid communication with an inlet channel 232. The inlet channel 232 is fluidically coupled to an inlet conduit 234. The inlet conduit 234 is coupled to the coolant source 221. Each of the fluid channels 231 and the inlet channels 232 is sealed by a cover plate 236. The cover plate 236 may be made of the same material as the disk 260 or aluminum and may be welded or otherwise bonded to the disk 260 to seal the fluid channels 231 and the inlet conduits 234. Although not shown, outlet conduits similar to the inlet conduits 234 are provided in the substrate support 115 so that cooling fluid can be recirculated therein.

[0034] A portion of the inlet duct 234 is formed by a tubular member 238. The tubular member 238 is formed from a dielectric material such as a ceramic material. Seals 240 are provided at the ends of the tubular member 238 adjacent to the cover plate 236 and the base plate 215. The tubular member 238 prevents arcing caused by the cooling fluid flowing therethrough. The tubular member 238 also thermally insulates the dielectric plate 210 from the relatively cool cooling fluid flowing therethrough, thereby preventing cracking of the dielectric plate 210.

[0035] The substrate support 115 further includes a plurality of lift pins 242 ( Figure 2A Only one is shown in FIG. 1 ). Each of the lifting rods 242 is movably disposed in a dielectric bushing 244. Each of the lifting rods 242 can be formed of a ceramic material (such as AlN, sapphire, quartz, etc.). The dielectric bushing 244 is provided to each of the disk 260, the dielectric plate 210, and the base plate 215 or passes through them. The dielectric bushing 244 is made of a polymer material such as polytetrafluoroethylene (PTFE). The dielectric bushing 244 includes an opening 246 along its length, in which the lifting rods 242 are guided. The size of the opening 246 is slightly larger than the size (diameter) of the lifting rods 242 so as to form a conductive path in the dielectric bushing 244. For example, the opening 246 is coupled to the variable pressure system 120 to provide vacuum conduction between the processing space 160 and to the variable pressure system 120 through the dielectric bushing 244. The conductive path provided by the opening 246 prevents arc discharge of the lifting rods. The dielectric bushing 244 includes a plurality of steps 248, which are sections of varying diameters. The steps 248 reduce arcing between the disk 260 and the base plate 215 by increasing the length of the path that electricity can travel and introducing angular turns along the path.

[0036] The substrate support 115 also includes a plurality of fastener devices 250 (only one is shown). The fastener devices 250 are used to attach the disk 260 to the dielectric plate 210. Each fastener device 250 includes a fastener 252, a washer 254, and a fastener cap 256 (the washer 254 and the fastener cap 256 are connected in a manner similar to the embodiment of the present invention). Figure 2B ). When fastener 252 is tightened, washer 254 is pressed against surface 258 of opening 268 formed in dielectric plate 210. Washer 254 and fastener 252 are made of a metal material such as stainless steel. Washer 254 includes rounded upper corners 262. Rounded upper corners 262 prevent cracking of the dielectric plate 210 material when fastener 252 is tightened.

[0037] Fastener cap 256 is used to fill the remainder of opening 268 of dielectric plate 210. Fastener cap 256 includes a pocket 264 sized to receive the head of fastener 252. Fastener cap 256 is formed from a dielectric material, such as a polymer, for example, polyetheretherketone (PEEK). The outer surface of fastener cap 256 includes a step 266. Step 266 reduces arcing between disk 260 and base plate 215 by increasing the path length that electricity can travel.

[0038] The substrate support 115 also includes a plurality of gaps between its layers. A first gap 270 is disposed between the disk 260 and the dielectric plate 210. A second gap 272 is disposed between the dielectric plate 210 and the base plate 215. The first gap 270 and the second gap 272 are in fluid communication with a gas source (not shown). Fluid from the gas source can flow through the first gap 270 and the second gap 272 to prevent condensation between adjacent layers. The fluid in the first gap 270 and the second gap 272 is sealed at the ends of the substrate support 115 by an edge ring. The edge ring can be sized to provide controlled leakage of the fluid from the first gap 270 and the second gap 272.

[0039] method

[0040] Embodiments of the present disclosure generally relate to methods for processing substrates, such as processes for forming a hard mask layer on a substrate. Conventional methods typically use a gas mixture of argon and / or helium during plasma ignition, which can result in damage to the underlying layer. In contrast, the embodiments described herein utilize a carbon-containing gas (with or without a non-reactive gas) to ignite a plasma to form an intermediate / initiation layer on a substrate while electrostatically clamping the substrate. This intermediate layer formation operation using low RF bias power prevents Ar ions from bombarding the underlying layer during pre-clamping and acts as a barrier (intermediate / initiation) layer to prevent high-energy bombardment of CH2+ ions during deposition, as determined by transmission electron microscopy images. Since, for example, the RF bias power used during the intermediate layer formation operation is lower relative to the main deposition operation, the CH2+ ions also do not negatively impact the underlying layer. During the main deposition operation, a carbon-containing gas (with or without a non-reactive gas) can also be used to form a carbon hard mask. In addition, the resulting hard mask film properties are not affected by this thin carbon-containing initiation layer (formed during plasma ignition). Typically, the sp of the carbon-containing initiation layer is 3 The content is lower than that of the layer formed from the main deposition operation and the thickness is less than about 100 Additionally, using a carbon-containing gas plasma ignition, with or without a non-reactive gas, helps mitigate damage to the underlying layer. As described below, the chucking / initiation layer is formed at a lower RF bias power than the main deposition operation.

[0041] Figure 3 3 is a flow chart illustrating selected operations of an example process 300 for forming a hardmask layer on a substrate, in accordance with at least one embodiment of the present disclosure. The process eliminates (or at least mitigates) underlying layer damage during formation of a carbon hardmask and improves adhesion between the hardmask and the underlying layer on which the hardmask is formed.

[0042] The process 300 includes introducing (e.g., transferring, transporting, etc.) a substrate into a processing area of ​​a substrate processing chamber at operation 310. As an example, a substrate (e.g., substrate 145) is transferred into the processing chamber 100 and onto the substrate support 115 by any suitable means, such as through the substrate transfer port 185. Figure 1 , the substrate support 115 can be adjusted to a processing position by an actuator 175. The substrate support 115 includes an electrostatic chuck, such as electrostatic chuck 230. The substrate can include one or more materials such as nitrides, oxides, silicon, and / or metals (e.g., tungsten, molybdenum, titanium, etc.).

[0043] The process 300 further includes flowing one or more process gases into the processing volume within the PECVD chamber at operation 320. As an example, the one or more process gases from one or more sources are provided to the processing volume 160 through, for example, a showerhead 135, such that the one or more process gases are uniformly distributed within the processing volume 160. In one example, the plurality of inlets 144 can be radially distributed around the spacer 110, and the gas flow to each of the plurality of inlets 144 can be individually controlled to further promote gas uniformity within the processing volume 160.

[0044] The process gas includes one or more carbon-containing compounds. Additionally or alternatively, the process gas is formed from one or more carbon-containing compounds. For example, a compound that is not in a gaseous state at standard temperature and pressure can be converted into a carbon-containing gas. Thus, in some examples, the carbon-containing gas includes the carbon-containing compound, or the carbon-containing gas is formed from the carbon-containing compound, or a combination thereof.

[0045] Non-limiting examples of carbon-containing compounds include hydrocarbons, aromatic hydrocarbons, and halogenated compounds. In some embodiments, the carbon number of the carbon-containing compound is, for example, C1-C 100 , such as C1-C 40 , such as C1-C 20 , such as C1-C 10 The carbon-containing compound may be linear or branched, cyclic or acyclic, and / or substituted or unsubstituted. Substituted means that at least one hydrogen atom of the carbon-containing compound is replaced by at least one heteroatom (such as a halogen, for example, fluorine (F), chlorine (Cl), bromine (Br) and / or iodine (I)) or a heteroatom-containing group (such as a functional group, for example -NR * 2. -OR * 、-SiR * 3. -GeR * 3, where each R * The carbon-containing compound is independently hydrogen, or a linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbon.

[0046] Non-limiting examples of hydrocarbons include, but are not limited to, hydrocarbons having the empirical formula C n H 2n+2 Alkanes with the empirical formula C n H 2n The olefin and the empirical formula C n H 2n-2Alkynes. Each of alkanes, alkene and alkynes can be straight or branched, cyclic or acyclic, aromatic or non-aromatic, substituted or unsubstituted. The non-limiting examples of alkanes include for example methane, ethane and propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane and isomers of eicosane. The non-limiting examples of alkene include for example ethene and isomers of propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecane, hexadecane, heptadecane, octadecane, nonadecane and eicosane. Non-limiting examples of alkynes include, for example, acetylene, and isomers of propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, undecyne, dodecyne, tridecyne, tetradecyne, pentadecyne, hexadecyne, heptadecyne, octadecyne, nonadecyne, and eicosyne.

[0047] Non-limiting examples of aromatic hydrocarbons include, but are not limited to, C4-C 30 Aromatic hydrocarbons, such as C6-C 20 Aromatic hydrocarbons, such as benzene, toluene, xylene and naphthalene. Aromatic hydrocarbons may be unsubstituted or substituted, wherein at least one hydrogen atom of the aromatic hydrocarbon is replaced by at least one heteroatom (such as a halogen, e.g., F, Cl, Br and / or I) or a heteroatom-containing group (such as a functional group, e.g., -NR * 2. -OR * 、-SiR * 3. -GeR * 3, where each R * are independently hydrogen, or linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbon).

[0048] Non-limiting examples of halogenated compounds include, but are not limited to, compounds having the empirical formula C n H x X' (2n+2-x) Compounds wherein X'=F, Cl, Br and / or I, and n=1-100 (such as 1-40, such as 1-30, such as 1-20, such as 1-10, such as 1-6). Illustrative but non-limiting examples of halogenated compounds include CF4, CH2F2, C4F6, or combinations thereof.

[0049] In some embodiments, the process gas further includes one or more non-reactive gases. Illustrative but non-limiting examples of non-reactive gases include helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn), or combinations thereof.

[0050] Process 300 further includes forming an energized process gas from the process gas at operation 330. The energized process gas is generated from a plasma under plasma conditions. Here, for example, RF power source 165 and / or RF power source 170 can provide RF power at any suitable frequency or power level for plasma generation. The RF power generates an electromagnetic field that energizes the process gas within processing volume 160. Non-limiting examples of process conditions for generating a plasma are provided below.

[0051] The process 300 further includes electrostatically clamping the substrate to a substrate support at operation 340 and depositing a first carbon-containing layer on the substrate while electrostatically clamping the substrate at operation 350. A hardmask layer is then formed by depositing a second carbon-containing layer on the substrate at operation 360. The first carbon-containing layer can serve as a barrier (intermediate / starting) layer to prevent high-energy bombardment of CH ions during the main deposition step of operation 360.

[0052] Various operations of the example processes described herein (eg, process 300 ) include one or more process parameters as described below.

[0053] The temperature of the substrate may have a temperature of about 100° C. or less, such as from about −40° C. to about 100° C., such as from about −30° C. to about 50° C. or from about −40° C. to about 10° C. In at least one embodiment, the temperature of the substrate is in a range from T1 to T2 (in degrees Celsius), wherein each of T1 and T2 is independently about −40, about −35, about −30, about −25, about −20, about −15, about −10, about −5, about 0, about 5, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95, or about 100, as long as T1 <T2。

[0054] The pressure within the processing space can be about 500 mTorr or less, such as about 400 mTorr or less, such as about 300 mTorr or less, such as about 200 mTorr or less, such as about 100 mTorr or less, such as about 50 mTorr or less, such as about 20 mTorr or less, such as from about 1 mTorr to about 10 mTorr, from about 4 mTorr to about 10 mTorr, or from about 5 mTorr to about 15 mTorr. In at least one embodiment, the pressure within the processing volume is in the range of from P1 to P2 (in millitorr), where each of P1 and P2 is independently about 0.5 millitorr, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, about 20, about 25, about 50, about 100, about 200, about 300, about 400, or about 500, as long as P1 <P2。

[0055] The flow rate of the one or more carbon-containing gases entering the processing volume can be about 5000 standard cubic centimeters per minute (sccm) or less, such as from about 20 sccm to about 5000 sccm for a 300 mm sized substrate, such as from about 50 sccm to about 200 sccm, such as from about 80 sccm to about 160 sccm. In at least one embodiment, for a 300 mm sized substrate, the flow rate of the one or more carbon-containing gases is in the range of Flow Rate 1 to Flow Rate 2 (in sccm), wherein each of Flow Rate 1 and Flow Rate 2 is independently about 20, about 30, about 40, about 50, about 60, about 70, about 80, about 90, about 100, about 110, about 120, about 130, about 140, about 150, about 160, about 170, about 180, about 190, about 200, about 210, about 220, about 230, about 240, about 250, about 500, about 1,000, about 1,500, about 2,000, about 2,500, about 3,000, about 3,500, about 4,000, about 4,500, or about 5,000, as long as Flow Rate 1 < Flow Rate 2.

[0056] In embodiments using one or more non-reactive gases, the flow rate of the one or more non-reactive gases into the processing volume can be about 3,000 sccm or less, such as about 500 sccm or less, such as about 250 sccm or less, such as from about 0 sccm to about 100 sccm, such as from about 1 to about 50 sccm, for a 300 mm sized substrate. In at least one embodiment, for a 300 mm sized substrate, the flow rate of the one or more non-reactive gases ranges from flow rate 3 to flow rate 4 (in sccm), wherein each of flow rate 3 and flow rate 4 is independently about 0, about 1, about 5, about 10, about 20, about 30, about 40, about 50, about 60, about 70, about 80, about 90, about 100, about 110, about 120, about 130, about 140, about 150, about 160, about 170, about 180, about 190, about 200, about 210, about 220, about 230, about 240, about 250, about 500, about 1,000, about 1,500, about 2,000, about 2,500, or about 3,000, as long as flow rate 3 is less than flow rate 4.

[0057] In embodiments using one or more non-reactive gases, the flow rate ratio of the carbon-containing gas(es) to the non-reactive gas(es) may be about 0.05 or greater, such as from about 0.1 to about 100, such as from about 0.5 to about 50, such as from about 1 to about 10, for a 300 mm sized substrate. In at least one embodiment, for a 300 mm sized substrate, the flow rate ratio of the carbon-containing gas(es) to the non-reactive gas(es) is in a range from Ratio 1 to Ratio 2, wherein each of Ratio 1 and Ratio 2 is independently about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 1, about 2, about 5, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95, or about 100, as long as Ratio 1 < Ratio 2.

[0058] The RF source power applied to the cover plate (e.g., cover plate 125) can be from about 100 watts (W) to about 10,000 W, such as from about 500 W to about 5,000 W, such as from about 1,000 W to about 2,000 W or from about 2,500 W to about 4,000 W. In at least one embodiment, the RF power is in the range of from Power 1 to Power 2 (in W), wherein each of Power 1 and Power 2 is independently about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 900, about 1,000, about 1,500, about 2,000, about 2,500, about 2,600, about 2,700, about 2,800, about 2,900, about 3,000, about 4,000, or about 5,000. ,100, about 3,200, about 3,300, about 3,400, about 3,500, about 3,600, about 3,700, about 3,800, about 3,900, about 4,000, about 4,500, about 5,000, about 5,500, about 6,000, about 6,500, about 7,000, about 7,500, about 8,000, about 8,500, about 9,000, about 9,500 or about 10,000 W, as long as Power 1 < Power 2.

[0059] The RF bias power applied to the substrate support during deposition may be from about 100 watts (W) to about 10,000 W, such as from about 500 W to about 5,000 W, such as from about 1,000 W to about 2,000 W or from about 2,500 W to about 4,000 W. In at least one embodiment, the RF bias power during deposition is in the range from Power 3 to Power 4 (in W), wherein each of Power 3 and Power 4 is independently about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 900, about 1,000, about 1,500, about 2,000, about 2,500, about 2,600, about 2,700, about 2,800, about 2,900, about 3,000, or about 4,000. , about 3,100, about 3,200, about 3,300, about 3,400, about 3,500, about 3,600, about 3,700, about 3,800, about 3,900, about 4,000, about 4,500, about 5,000, about 5,500, about 6,000, about 6,500, about 7,000, about 7,500, about 8,000, about 8,500, about 9,000, about 9,500 or about 10,000, as long as Power 3 < Power 4.

[0060] The RF bias power during plasma ignition may be from about 100 watts (W) to about 1,000 W, such as from about 100 W to about 800 W, such as from about 200 W to about 500 W. In at least one embodiment, the RF bias power during plasma ignition is in a range from Power 5 to Power 6 (in W), wherein each of Power 5 and Power 6 is independently about 10, about 50, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450, about 500, about 550, about 600, about 650, about 700, about 750, about 800, about 850, about 900, about 850, or about 1,000, as long as Power 5 < Power 6.

[0061] The substrate support may be biased by providing RF power at a frequency of at least about 300 kHz, such as from about 400 kHz to about 120 MHz or from about 300 kHz to about 60 MHz, such as from about 1 MHz, such as from about 10 MHz. The frequency may be pulsed.

[0062] The plasma density of the employed plasma may be of the order of about 10 ions / cm 3 or greater, such as from about 100 ions / cm 3 to about 1×10 15 ions / cm 3 , such as from about 1×10 7 ions / cm 3 to about 1×10 15 ions / cm 3 , such as from about 1×10 8 ions / cm 3 to about 1×10 14 ions / cm 3 , such as from about 1×10 9 ions / cm 3 to about 1×10 13 ions / cm 3 , such as from about 1×10 10 ions / cm 3 to about 1×10 12 ions / cm 3 In at least one embodiment, the plasma density (PD) is in the range from time 1 to time 2 (in seconds), where each of PD1 and PD2 is independently about 1 ion / cm 3 , about 10 ions / cm 3 , about 100 ions / cm 3 , about 1×10 3 ions / cm 3 , about 1×10 4 ions / cm3 , about 1×10 5 ions / cm 3 , about 1×10 6 ions / cm 3 , about 1×10 7 ions / cm 3 , about 1×10 8 ions / cm 3 , about 1×10 9 ions / cm 3 , about 1×10 10 ions / cm 3 , about 1×10 11 ions / cm 3 , about 1×10 12 ions / cm 3 , about 1×10 13 ions / cm 3 , about 1×10 14 ions / cm 3 or about 1×10 15 ions / cm 3 , provided that PD1 < PD2. The plasma density can be measured in the processing region of the substrate processing chamber.

[0063] The deposition time of the carbon-containing layer can be about 1 second or more, such as from about 1 second to about 2000 seconds, such as from about 1 second to about 1000 seconds, or from about 1000 seconds to about 1500 seconds. In at least one embodiment, the deposition time is in the range from time 1 to time 2 (in seconds), where each of time 1 and time 2 is independently about 1, about 10, about 30, about 60, about 90, about 120, about 150, about 200, about 240, about 300, about 360, about 420, about 480, about 540, about 600, 660, about 720, about 780, about 840, about 900, about 960, about 1000, about 1020, about 1080, about 1140, about 1200, about 1260, about 1320, about 1380, about 1440, about 1500, about 1560, about 1620, about 1680, about 1740, about 1800, about 1860, about 1920, about 1980 or about 2000, provided that time 1 < time 2.

[0064] The thickness of the formed carbon-containing layer can be about 25 angstroms or greater, such as from about 50 to about 50,000 such as from about 100 to about 25,000 In at least one embodiment, the carbon-containing layer thickness is in the range from thickness 1 to thickness 2 (in , about 14,000, about 15,000, about 16,000, about 17,000, about 18,000, about 19,000, about 20,000, about 21,000, about 22,000, about 23,000, about 24,000, about 25,000, about 26,000, about 27,000, about 28,000, about 29,000, about 30,000, about 31,000, about 32,000, about 33,000, about 34,000, about 35,000, about 36,000, about 37,000, about 38,000, about 39,000, about 40,000, about 41,000, about 42,000, about 43,000, about 44,000, about 45,000, about 46,000, about 47,000, about 48,000, about 49,000, about 50, 000, about 24,000, about 25,000, about 26,000, about 27,000, about 28,000, about 29,000, about 30,000, about 31,000, about 32,000, about 33,000, about 34,000, about 35,000, about 36,000, about 37,000, about 38,000, about 39,000, about 40,000, about 41,000, about 42,000, about 43,000, about 44,000, about 45,000, about 46,000, about 47,000, about 48,000, about 49,000 or about 50,000, as long as Thickness 1 < Thickness 2.

[0065] The deposition rate of the carbon-containing layer can be about 1 angstrom per minute ( / minute) or higher, such as from about 1 / minute to about 5,000 / minute, such as from about 10 / minute to about 3,000 / minute, such as from about 100 / minute to about 2,000 In at least one embodiment, the deposition rate of the carbon-containing layer is increased from DR1 to DR2 (in / minute), wherein each of DR1 and DR2 is independently about 1, about 10, about 50, about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 900, about 1,000, about 1,100, about 1,200, about 1,300, about 1,400, about 1,500, about 1,600, about 1,700, about 1,800, about 1,900, about 2,000, about 2,100, about 2,200, about 2,300, about 2,400 0, about 2,500, about 2,600, about 2,700, about 2,800, about 2,900, about 3,000, about 3,100, about 3,200, about 3,300, about 3,400, about 3,500, about 3,600, about 3,700, about 3,800, about 3,900, about 4,000, about 4,100, about 4,200, about 4,300, about 4,400, about 4,500, about 4,600, about 4,700, about 4,800, about 4,900 or about 5,000, as long as DR1 <DR2。

[0066] In some embodiments, the deposited carbon-containing layer has at least 10% sp 3 - hybrid atoms. That is, the sp 3 - The mixed content may be at least 10%. 3 - The mixed content can be from about 1% to about 100%, such as from about 5% to about 90%, such as from about 10% to about 75%, such as from about 25% to about 50% or at least about 60%. In at least one embodiment, the sp of the carbon-containing layer 3 -The mixed content is within the range of from content 1 to content 2 (in %), wherein each of content 1 and content 2 is independently about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95 or about 100, as long as content 1 < content 2.

[0067] New and improved processes and structures are described herein that overcome one or more deficiencies of conventional methods for forming hard molds. The embodiments described herein can achieve, for example, reduced substrate damage during hard mold formation and improved adhesion between the hard mold and the substrate. Consequently, the embodiments described herein can achieve, for example, improved device performance.

[0068] As can be seen from the above general description and specific examples, although the forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not intended to limit the present disclosure thereby. Likewise, the term "comprising" is considered to be synonymous with the term "including." Likewise, when a composition, element, or group of elements is preceded by the transitional phrase "comprising," it should be understood that we also contemplate the transitional phrases "essentially consisting of," "consisting of," "selected from a group consisting of," or "is" preceding the narration of the composition, element, or group of elements, and vice versa.

[0069] For purposes of the present disclosure, unless otherwise indicated, all numerical values ​​in the detailed description and claims herein are modified as "about" or "approximately" the stated value, and take into account experimental error and variations that would be expected by a person of ordinary skill in the art.

[0070] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be understood that, unless otherwise indicated, ranges are contemplated that include any combination of two values, for example, any lower value combined with any higher value, any two lower values ​​combined, and / or any two higher values ​​combined. Certain lower limits, upper limits, and ranges appear in one or more of the following claims.

[0071] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, the scope of which is determined by the claims hereinafter appended.

Claims

1. A process for forming a hard mask on a substrate, comprising: introducing the substrate into a processing volume of a plasma enhanced chemical vapor deposition (PECVD) chamber, the substrate being positioned on a substrate support, the substrate support comprising an electrostatic chuck; Depositing a first carbon-containing layer on the substrate while electrostatically clamping the substrate to the substrate support, the first carbon-containing layer having a thickness of approximately or less in thickness, wherein depositing the first carbon-containing layer comprises: flowing a process gas into the process space within the PECVD chamber, the process gas comprising a carbon-containing gas; and igniting a plasma with the process gas to deposit the first carbon-containing layer by applying a first RF bias power to the electrostatic chuck, the first RF bias power being from about 200 W to about 500 W; and The hardmask is formed by depositing a second carbon-containing layer on the first carbon-containing layer while electrostatically clamping the substrate to the substrate support, the second carbon-containing layer having a thickness of about to about A thickness of , wherein depositing the second carbon-containing layer comprises: flowing the process gas into the process space within the PECVD chamber; and A second RF bias power is applied to the electrostatic chuck to deposit the second carbon-containing layer, the second RF bias power being about 1,000 W to about 10,000 W.

2. The process of claim 1 , wherein the carbon-containing gas comprises or is formed from a carbon-containing compound, and wherein the carbon-containing compound is a substituted or unsubstituted C1-C 40 Hydrocarbons, substituted or unsubstituted C6-C 20 Aromatic hydrocarbons, C1-C 40 halogenated hydrocarbons, or combinations thereof.

3. The process of claim 2, wherein the carbon-containing compound comprises an alkyne.

4. The process of claim 3, wherein the carbon-containing compound comprises acetylene.

5. The process of claim 2, wherein the process gas further comprises a non-reactive gas.

6. The process of claim 5, wherein the carbon-containing compound comprises acetylene and the non-reactive gas comprises helium.

7. The process of claim 1, wherein the first carbon-containing layer, the second carbon-containing layer, or both are deposited while the substrate is maintained at a temperature of about -40°C to about 40°C.

8. The process of claim 1, wherein the first carbon-containing layer, the second carbon-containing layer, or both comprise about 60% or more sp 3 -Mixed atoms.

9. The process of claim 1, wherein: depositing the first carbon-containing layer while the processing space is maintained at a first pressure; and The second carbon-containing layer is deposited while the processing space is maintained at a second pressure.

10. The process of claim 9, wherein the first pressure is from about 20 mTorr to about 500 mTorr, and the second pressure is from about 1 mTorr to about 10 mTorr.

11. A process for forming a hard mask on a substrate, comprising: positioning the substrate within a processing volume of a plasma enhanced chemical vapor deposition (PECVD) chamber, the substrate being on an electrostatic chuck; Depositing a first carbon-containing layer on the substrate while electrostatically clamping the substrate, the first carbon-containing layer having a thickness of about or less in thickness, wherein depositing the first carbon-containing layer comprises: A process gas is flowed into the process space within the PECVD chamber, wherein the process gas comprises a carbon-containing gas, wherein the carbon-containing gas comprises a carbon-containing compound, or the carbon-containing gas is formed from a carbon-containing compound, and wherein the carbon-containing compound is a substituted or unsubstituted C1-C 40 Hydrocarbons, substituted or unsubstituted C6-C 20 Aromatic hydrocarbons, C1-C 40 halogenated hydrocarbons, or combinations thereof; operating the processing volume at a first pressure of about 20 mTorr to about 500 mTorr; and igniting a plasma with the process gas to deposit the first carbon-containing layer by applying a first RF bias power to the electrostatic chuck, the first RF bias power being from about 200 W to about 500 W; and The hard mask is formed by depositing a second carbon-containing layer on the first carbon-containing layer while electrostatically clamping the substrate, the second carbon-containing layer having a thickness of about to about A thickness of , wherein depositing the second carbon-containing layer comprises: allowing the process gas to flow into the process space within the PECVD chamber; operating the processing volume at a second pressure of about 0.5 mTorr to about 10 mTorr; and A second RF bias power is applied to the electrostatic chuck to deposit the second carbon-containing layer, the second RF bias power being about 1,000 W to about 10,000 W.

12. The process of claim 11, wherein the carbon-containing compound comprises an alkyne.

13. The process of claim 11, wherein the process gas further comprises one or more non-reactive gases.

14. The process of claim 11, wherein the first carbon-containing layer, the second carbon-containing layer, or both are deposited while the substrate is maintained at a temperature of about -40°C to about 10°C.

15. The process of claim 11, wherein the first carbon-containing layer, the second carbon-containing layer, or both comprise about 60% or more sp as determined by Raman spectroscopy. 3 -Mixed atoms.

16. A process for forming a hard mask on a substrate, comprising: positioning the substrate within a processing volume of a plasma enhanced chemical vapor deposition (PECVD) chamber, the substrate being on an electrostatic chuck; Depositing a first carbon-containing layer on the substrate while electrostatically clamping the substrate, the first carbon-containing layer having a thickness of about or less in thickness, wherein depositing the first carbon-containing layer comprises: A process gas is flowed into the process space in the PECVD chamber, wherein the process gas includes a carbon-containing gas and a non-reactive gas, wherein the carbon-containing gas includes or is formed from a carbon-containing compound, and the carbon-containing compound includes substituted or unsubstituted Cl-C 20 hydrocarbons, and wherein the non-reactive gas comprises He, Ne, Ar, or a combination thereof; operating the processing volume at a pressure of about 20 mTorr to about 500 mTorr; and igniting a plasma with the process gas to deposit the first carbon-containing layer by applying a first RF bias power to the electrostatic chuck, the first RF bias power being from about 200 W to about 500 W; and The hard mask is formed by depositing a second carbon-containing layer on the first carbon-containing layer while electrostatically clamping the substrate, the second carbon-containing layer having a thickness of about to about A thickness of , wherein depositing the second carbon-containing layer comprises: allowing the process gas to flow into the process space within the PECVD chamber; operating the processing volume at a pressure of about 0.5 mTorr to about 10 mTorr; and applying a second RF bias power to the electrostatic chuck to deposit the second carbon-containing layer, the second RF bias power being from about 1000 W to about 10000 W, The first carbon-containing layer, the second carbon-containing layer, or both are deposited while the substrate is maintained at a temperature of about -40°C to about 40°C.

17. The process of claim 16, wherein the first carbon-containing layer, the second carbon-containing layer, or both are deposited while the substrate is maintained at a temperature of about -40°C to about 10°C.

18. The process of claim 16, wherein the first carbon-containing layer, the second carbon-containing layer, or both comprise about 60% or more sp as determined by Raman spectroscopy. 3 -Mixed atoms.

19. The process of claim 16, wherein the carbon-containing compound is an alkyne and the non-reactive gas comprises He.

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